WO2008072765A1 - Polymère contenant du fluor et composition de résine - Google Patents

Polymère contenant du fluor et composition de résine Download PDF

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Publication number
WO2008072765A1
WO2008072765A1 PCT/JP2007/074235 JP2007074235W WO2008072765A1 WO 2008072765 A1 WO2008072765 A1 WO 2008072765A1 JP 2007074235 W JP2007074235 W JP 2007074235W WO 2008072765 A1 WO2008072765 A1 WO 2008072765A1
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Prior art keywords
formula
hydrogen
polymer
fluorine
carbon atoms
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PCT/JP2007/074235
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English (en)
Japanese (ja)
Inventor
Hisao Oikawa
Koji Ohguma
Kenya Ito
Mikio Yamahiro
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Chisso Corporation
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Priority to KR20097012338A priority Critical patent/KR101494347B1/ko
Priority to AT07850723T priority patent/ATE543846T1/de
Priority to EP07850723A priority patent/EP2096128B1/fr
Priority to JP2008549391A priority patent/JPWO2008072765A1/ja
Priority to US12/519,354 priority patent/US7989560B2/en
Publication of WO2008072765A1 publication Critical patent/WO2008072765A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/068—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/148—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D155/00—Coating compositions based on homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C09D123/00 - C09D153/00

Definitions

  • the present invention relates to a polymer containing fluorine. Furthermore, this invention relates to the surface modifier containing the resin composition containing a fluorine-type polymer. Furthermore, the present invention relates to a film obtained with a surface modifier containing a resin composition containing a fluoropolymer.
  • Patent Document 1 reports a water-repellent coating material in which a radically polymerizable monomer containing a fluoroalkyl group is dispersed in a thermosetting binder resin. Adhesiveness to a substrate having low compatibility with the resin was also insufficient.
  • Patent Document 2 proposes a plastic product in which a silicone resin is mixed. However, the oil repellency is low because the compatibility between the silicone resin and other resins is low.
  • Patent Document 3 As a compound of a fluorine-based and silicone-based compound, a coating agent composition containing a silicone resin having a fluoroalkyl group is reported in Patent Document 3. The solubility in general organic solvents is low, and a fluorine-based drug is disclosed. I had to use a solvent! And! /.
  • Patent Document 1 JP-A-7-102187
  • Patent Document 2 Japanese Patent Publication No. 4 103668
  • Patent Document 3 JP-A-9 151357
  • the present invention provides water / oil repellency, antifouling properties, non-adhesiveness, release properties, slipperiness, wear resistance, corrosion resistance, It is an object of the present invention to provide a new polymer that is excellent in electrical insulation, antireflection properties, flame retardancy, antistatic properties, chemical resistance, weather resistance and the like and can be used as a surface modifier.
  • the present inventors have a structural unit derived from fluorosilsesquioxane having one addition polymerizable functional group in the molecule and an addition polymerizable functional group.
  • An addition copolymer comprising a structural unit derived from an organopolysiloxane and a structural unit derived from an addition-polymerizable monomer containing a group having active hydrogen as an essential component has excellent water and oil repellency, and has a surface It was found useful as a modifier.
  • the present invention relates to a structural unit derived from fluorosilsesquioxane having one addition polymerizable functional group in the molecule, a structural unit derived from organopolysiloxane having an addition polymerizable functional group, Provided is an addition copolymer comprising as an essential component a structural unit derived from an addition polymerizable monomer containing a group having active hydrogen. Furthermore, it provides a new use of the fluoropolymer. New uses include, for example, a constitutional unit derived from fluorosilsesquioxane having one addition polymerizable functional group in the molecule, and a constitution derived from onorenopolysiloxane having an addition polymerizable functional group. For example, the use of an addition copolymer as a surface modifier, which includes a unit and a structural unit derived from an addition-polymerizable monomer containing a group having active hydrogen as essential components.
  • the present invention relates to the following polymers, resin compositions, and films.
  • each R ⁇ R 7 is independently a linear or branched fluoroalkyl having 120 carbon atoms in which any methylene may be replaced by oxygen; at least 1 Fluoroaryl having 6 20 carbons in which two hydrogens have been replaced by fluorine or trifluoromethyl; or Fluoroarylalkyl having 720 carbons in which at least one hydrogen in the aryl has been replaced by fluorine or trifluoromethyl
  • a 1 represents an addition polymerizable functional group.
  • I ⁇ R 7 is independently selected from 3,3,3-trifluoropropyl, 3,3 ff
  • I ⁇ R 7 is independently 3,3,3-trifluoropropyl, 3,3 ff
  • n is an integer from !! to 1,000;
  • R, R, R, R, and R are each independently hydrogen, carbon number;!
  • An alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted aryl, optionally substituted with fluorine, and any CH— may be replaced with O or cycloalkylene, and optionally An arylalkyl composed of an alkylene in which hydrogen may be replaced by fluorine and any CH— may be replaced by O or cycloalkylene;
  • a 2 is an addition polymerizable functional group.
  • R 1 and R 2 forces in formula (2) are each independently hydrogen, phenyl, or alkyl having 1 to 8 carbon atoms, and any hydrogen may be replaced by fluorine;
  • R 5 is 1-20 carbon atoms and any hydrogen is replaced with fluorine /, Alkyl, aryl having 6 to 20 carbon atoms and arbitrary hydrogen may be replaced with fluorine, or 7 to 20 carbon atoms and arbitrary hydrogen being replaced with fluorine
  • R 1 and R 2 in the formula ( 2 ) are each independently methyl, phenyl or 3, 3, 3 -trifluoropropyl; R 3 and R 4 are each independently methyl or phenyl.
  • R 5 is methyl, ethyl, propyl, butyl, isobutyl, phenole, 3,3,3-trifluoropropinore, 3,3,4,4,4-pentafluororebutino Le, 3, 3, 4, 4, 5, 5, 6, 6, 6-Nonaphnore Hexyl, Tridecafluo- 1,1,2,2-Tetrahydrootatil, Heptadecafluo-1, 1,2,2 -Tetrahydrodecyl, helicosafluorine- 1,1,2,2-tetrahydrododecyl, pentapropyl, pentafluorophenylpropyl, pentafluorophenyl, or ⁇ , ⁇ , ⁇ -The polymer according to [5],
  • a 1 in formula (1) is represented by the following formula (3) or (5)
  • a 2 in formula (2) is represented by any of the following formulas (3), (4), or (5)
  • Y 1 represents alkylene having 2 to 10 carbon atoms
  • R 6 is hydrogen, alkyl having! To 5 carbons, or aryl having 6 to 10 carbon atoms
  • R 7 is hydrogen, carbon number;! To 5 alkyl, or 6 to 10 carbon atom
  • X 1 is an arylene having 2 20 carbon atoms
  • Y is OCH CH -OCHCH CH or OCH CH (CH) —
  • p is an integer of 0 3 and in formula (5), Y 2 is a single bond or a carbon number
  • Y 1 represents alkylene having 26 carbon atoms
  • R 6 represents hydrogen or methyl
  • X 1 represents CH 2 CH 2 CH 2
  • Y represents OCH 2 CH 3
  • Y 2 in the formula (5) represents a single bond or alkylene having 1 or 2 carbon atoms.
  • a basic unit having an active hydrogen of the structural unit C An amino group, a carboxyl group, or a hydroxyl group [1] to [;
  • a resin composition comprising the polymer according to any one of [1] to [; 13] and one or more kinds of resins selected from thermoplastic resins and / or thermosetting resins.
  • the fluorine-based polymer of the present invention and the resin composition containing the polymer are water- and oil-repellent, antifouling, non-adhesive, releasability, slipperiness, abrasion resistance, and corrosion resistance. It has excellent electrical insulation, antireflection properties, flame retardancy, antistatic properties, chemical resistance, weather resistance, etc., for example, it can be used as a surface modifier by coating on the surface of various base materials. be able to.
  • addition polymerization means that addition polymerization is possible
  • addition polymerization monomer means a monomer capable of addition polymerization, and is addition polymerization
  • the functional group means a functional group capable of addition polymerization.
  • the polymer of the present invention contains a structural unit A, a structural unit B, a structural unit C and / or a structural unit D.
  • the structural unit A has one addition polymerizable functional group in the molecule.
  • the structural unit B is derived from an organopolysiloxane having an addition polymerizable functional group
  • the structural unit C is derived from an addition polymerizable monomer containing a group having an active hydrogen.
  • the structural unit D is derived from an addition polymerizable monomer other than the addition polymerizable monomer used as the structural unit A, the structural unit B, and the structural unit C. “Derived” means a polymerized residue when each monomer constitutes the polymer of the present invention.
  • the mole fraction (%) of the structural unit A in the polymer is represented by &
  • the mole fraction (%) of the structural unit B in the polymer is represented by 13
  • the mole fraction (%) of the structural unit D in the polymer is represented by (1; 0 ⁇ a ⁇ 100, 0 ⁇ b ⁇ l 00, 0 ⁇ c ⁇ 100, 0 ⁇ d, respectively.
  • ⁇ 100, a + b + c + d 100 is satisfied.
  • the polymer of the present invention includes, for example, fluorosilsesquioxane ( ⁇ ) having one addition polymerizable functional group in the molecule and organopolysiloxane (/ 3) having an addition polymerizable functional group.
  • the force S is obtained by copolymerizing an addition polymerizable monomer ( ⁇ ) containing a group having active hydrogen.
  • Fluorosylsesquioxane has a silsesquioxane skeleton in the molecular structure.
  • Silsesquioxane is represented by [(R-SiO 2)] (R is an optional substituent)
  • silsesquioxane It is a general term for xanthan.
  • the structure of this silsesquioxane depends on its Si-O-Si skeleton.
  • the cage structure is ⁇
  • fluorosilsesquio used in the present invention
  • Xane preferably has a cage structure of cage type [(R-SiO 2)].
  • the above fluorosilsesquioxane is characterized by having one addition polymerizable functional group. That is, one of the silsesquioxane [(R—SiO 2)]
  • Examples of the above-mentioned addition polymerizable functional group include: a group having a terminal olefin type or an internal olefin type radical polymerizable functional group; a group having a force thio polymerizable function group such as butyl ether or propenyl ether; In addition, a group having an anion polymerizable functional group such as bull carboxyl and cyanoacryloyl is included, and a radical polymerizable functional group is preferable.
  • the radical polymerizable functional group is not particularly limited as long as it is a radical polymerizing group.
  • a group containing (meth) acrylyl or styryl is preferable.
  • (meth) acryl is a general term for acrylic and methacryl and means acrylic and / or methacrylic. The same shall apply hereinafter.
  • radical polymerizable functional group having (meth) acryl examples include the group represented by the following formula (3).
  • ⁇ 1 represents an alkylene having 2 to 10 carbon atoms, preferably an alkylene having 2 to 6 carbon atoms, and more preferably an alkylene (propylene) having 3 carbon atoms.
  • R represents hydrogen, alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms, preferably hydrogen or alkyl having 1 to 3 carbon atoms, more preferably hydrogen or methyl.
  • the alkyl having 1 to 5 carbon atoms may be linear or branched.
  • examples of the radical polymerizable functional group having styryl include a group represented by the following formula (5).
  • Y 2 represents a single bond or alkylene having 1 to 10 carbon atoms, preferably a single bond or alkylene having 1 to 6 carbon atoms, more preferably a single bond or 1 or 2 carbon atoms. And particularly preferably a single bond or alkylene (ethylene) having 2 carbon atoms. Bulle is bonded to any carbon of the benzene ring, preferably bonded to the carbon in the para position with respect to Y 2 .
  • R other than is all fluoroalkyl, fluoroarylalkyl and / or fluoroaryl.
  • the above fluoroalkyl may be either linear or branched.
  • the fluorine-containing alkyl has 1 to 20 carbon atoms, preferably 3 to 14 carbon atoms.
  • any methylene of the fluoroalkyl may be replaced with oxygen.
  • methylene includes -CH-, -CFH- or -CF-. That is, “any methylene may be replaced by oxygen” means that —CH 2 —, —CFH—, or —CF 2 — may be replaced with —0—.
  • fluoroalkyl two oxygens are not bonded (-0-0-). That is, the fluoroalkyl may have an ether bond.
  • fluoroalkyl examples include 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5, 6,6,6-Nonafluohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrododecyl, hencosafluoro-1,1,2,2- Tetrahydrododecyl, pentacosafluo-1-1,1,2,2-tetrahydrotetradecyl, (3-heptafanololeisopropoxy) propyl and the like are included.
  • a force in which a perfluoroalkylethyl is preferably exemplified may be a group in which a fluoroalkyl group is bonded through —CH 2 —CH—, or a fluoroalkylene group is bonded through —CH—. It may be a group.
  • the fluoroarylalkyl is an alkyl containing fluorine-containing aryl, and preferably has 7 to 20 carbon atoms, more preferably 7 to 10;
  • the fluorine contained is preferably replaced by any one or more hydrogen power fluorine or trifluoromethyl in aryl.
  • aryl moieties include phenyl, naphthyl and the like, as well as heteroaryls, and examples of alkyl moieties include methyl, ethyl and propyl.
  • the fluoroaryl is one that is replaced by any one or more hydrogen power fluorine or trifluoromethyl in aryl, and the carbon number thereof is 6-20. More preferably 6.
  • force and carbyl include phenyl, naphthyl and hetero reels.
  • fluorophenyl such as pentafluorophenyl and trifluoromethylphenyl.
  • fluoroalkyl Of the above-mentioned fluoroalkyl, fluoroalkyl, or fluoroaryl contained in fluorosilsesquioxane, a preferred group is fluoroalkyl, more preferably perfluoroalkylethyl, and more preferably 3,3,3. -Trifluoro mouth pill, 3, 3, 4, 4, 5, 5, 6, 6, 6-Nonafluo hexyl or tridecafluor mouth-1, 1, 2, 2-
  • the preferred fluorosilsesquioxane has a T-type structure and has one attachment.
  • a 1 is added heavy synthetic functional groups, and each independently is preferably fixture R ⁇ R 7 is that a radical polymerizable officer functional groups described above, the aforementioned Furuoroarukiru ,
  • R i to R 7 in Formula (1) are each independently 3,3,3-trifluoropropyl, 3,3,4,4 ff
  • Organopolysiloxane typified by polydimethylsiloxane (hereinafter sometimes referred to as silicone or polysiloxane) has two types with polymerizable functional groups at both ends and one end, and both ends and one end have Functional groups include amide-containing hydroxyl groups, methacryloxy, carboxy
  • the organopolysiloxane at both ends can introduce a silicone component into the organic polymer main chain, and the organopolysiloxane at one end can graft a silicone component to the organic polymer side chain.
  • the polymer thus obtained has unique characteristics as a silicone, such as water repellency, mold release, slipperiness, low friction, antithrombogenicity, heat resistance, electrical properties, flexibility, oxygen permeability. It exhibits high resistance and radiation resistance, and is widely used in cosmetics and medical fields, especially in the field of electronic materials.
  • the organopolysiloxane (/ 3) having an addition polymerizable functional group which is a raw material monomer of the polymer of the present invention, preferably has a molecular structure represented by the following formula (2).
  • organopolysiloxane (/ 3) used in the present invention is the above formula (2), wherein n is;
  • R 2 , R 3 , R 4 , and R 5 are each independently hydrogen, carbon number ⁇ -30, any hydrogen can be replaced by fluorine, and any CH 1 is O or cyclo May be replaced by alkylene! /, Alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted aryl, and any hydrogen may be replaced by fluorine, and any CH— may be O or cycloalkylene
  • An arylalkyl composed of alkylene which may be replaced by A; and A 2 is an addition-polymerizable functional group.
  • the organopolysiloxane (/ 3) having an addition polymerizable functional group used in the present invention has hydrogen, phenyl or carbon number of 1 independently for each of R 1 and R 2 forces in the above formula (2).
  • ⁇ 8 is alkyl in which any hydrogen may be replaced by fluorine;
  • R 3 and R 4 forces, independently have 1 to 20 carbon atoms and any hydrogen may be replaced with fluorine! /, Alkyl, 6 to 20 carbon atoms with any hydrogen replaced with fluorine May be reels, or any hydrogen that has 7 to 20 carbon atoms and is replaced by fluorine.
  • V is arylalkyl
  • R 5 force Alkyl having 1 to 20 carbon atoms and arbitrary hydrogen being replaced by fluorine, aryl having 6 to 20 carbon atoms and arbitrary hydrogen being replaced by fluorine, or carbon number It is preferably an arylalkyl which is 7 to 20 and arbitrary hydrogen may be replaced by fluorine.
  • R 1 and R 2 in the above formula (2) are each independently methyl, phenyl, or 3, 3, 3-trifluoropropyl.
  • R 3 and R 4 are each independently methyl or phenyl;
  • R 5 is methyl, ethyl, propyl, butyl, isobutyl, phenyl, 3,3,3-trifluoropropyl, 3,3 , 4,4,4-pentafluorobutyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, tridecafluoro- 1,1,2,2-tetrahydroota Chill, heptadecafluor-1, 1,1,2,2-tetrahydrodecyl, hencosafluo-1, 1,2,2-tetrahydrododecyl, pentacosafluor-1, -1,2, orophenylpropyl, pentaflufluor
  • R 1 , R 2 , R 3 and R 4 are preferably methyl at the same time.
  • a 2 is preferably a radical polymerizable functional group.
  • a 2 preferably contains (meth) acrylic or styryl.
  • a 2 force The following formula (3), More preferably, it is any one of (4) and (5).
  • Y 1 represents an alkylene having 2 to 10 carbon atoms
  • R 6 is hydrogen, or carbon atoms;!, An arenoquinole having 5 carbon atoms, or an aryl having 6 to 10 carbon atoms
  • R 7 is hydrogen, alkyl having 15 carbons, or aryl having 6 to 10 carbons
  • X 1 is alkylene having 2 20 carbons
  • ⁇ is one OCH CH OCH ( CH 2) CH 3 or OCH 2 CH 3 (CH 2) —
  • p is an integer of 0 3
  • Y 2 represents a single bond or an alkylene having 1 to 10 carbon atoms.
  • the alkyl having 15 carbon atoms may be a straight chain or branched chain, or may be displaced! /.
  • Y 1 represents alkylene having 26 carbon atoms
  • R 6 represents hydrogen or methyl
  • X represents CH 2 CH 2 CH 3
  • Y represents OCH CH—
  • p represents 0 or 1
  • R 7 represents hydrogen or methyl
  • Y 2 in Formula (5) preferably represents a single bond or an alkylene having 1 or 2 carbon atoms.
  • organopolysiloxane (/ 3) preferably used in the present invention examples include Silaplane FM0711 (manufactured by Chisso Corporation), Silaplane FM0721 (manufactured by Chisso Corporation), Cylablane FM0725 (manufactured by Chisso Corporation), Sila Plane TM0701 (manufactured by Chisso Corporation), Cylab Lane TM0701T (manufactured by Chisso Corporation), etc. are included.
  • Active hydrogen is hydrogen bonded to an atom (eg, nitrogen atom, sulfur atom, oxygen atom) whose electronegativity value is greater than or equal to carbon among hydrogen atoms existing in the molecule of an organic compound. It is.
  • groups of the group having such an active hydrogen include OHSH-COOHNHNHCONHNHCONHNHCOO-Na + [CH (COOCH)] CHNOOOHSiOHB (OH) PHSH, etc. Amino and hydroxyl are preferred.
  • addition polymerizable monomer containing a group having active hydrogen examples include a group having active hydrogen as long as it is a compound having a group having active hydrogen and an addition polymerizable double bond in the molecule. Any of a compound, a vinylidene compound, and a vinylene compound may be sufficient. Preferably, it is an acrylic acid derivative or a styrene derivative containing a group having active hydrogen.
  • JP-A-9-20868 is disclosed. Mention may be made of the monomers mentioned in JP-A-2002-348344 and JP-A-2006-158961.
  • the carboxyl group-containing bull monomers include (meth) acrylic acid, (anhydrous) maleic acid, monoanolequinoleestenole maleate, fumanoleic acid, fumanoleic acid monoanorequinoreestenole, crotonic acid, itaconic acid, itaconic acid mono Examples include alkyl esters, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl esters, (meth) acrylic acid hexadecane and cinnamic acid.
  • hydroxyl group-containing bull monomer examples include a hydroxyl group-containing monofunctional bull monomer and a hydroxyl group-containing polyfunctional bull monomer.
  • hydroxyl group-containing monofunctional butyl monomer a butyl monomer having one butyl group is used.
  • hydroxystyrene N-methylol (meth) acrylamide, hydroxyethyl (methylate, polyethylene glycol mono (meth) acrylate, polypropylene Glycol mono (meth) acrylate, (meth) aryl alcohol, crotyl alcohol, isocrotinoleanolol, 1-butene 3 honore, 2 butene 1-honore, 2 butene 1, 4-zio- 1 nore, prono noregino Rheanoleconore, 2-hydroxyethinolev, lopeninoreethenore (2-propenoxyethanol), 16-hydroxyhexadecane metaatalylate and sucrose allyl ether, etc.
  • hydroxyl group-containing polyfunctional butyl monomer For example, a butyl monomer having a plurality of butyl groups is used.
  • amino group-containing butyl monomers examples include aminoethyl (meth) acrylate and aminoaminopro. Pyr (meth) acrylate, aminobutyl (meth) acrylate, amino hexyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) arylamine, crotyramine, aminostyrene, methyl ⁇ -acetoaminoacrylate, ⁇ Such as —arylphenolic diamine and 16-methacryloylhexadecanamine.
  • the addition polymerizable monomer ( ⁇ ), (13), ( ⁇ ), compatibility with a resin as an optional component, leveling properties, activity in the copolymer In order to control the content of the hydrogen-containing group and the like, the addition polymerizable monomer ( ⁇ ) other than the addition polymerizable monomer ( ⁇ ), (0), ( ⁇ ) is also optionally added as necessary. Can be used together.
  • the addition-polymerizable monomer ( ⁇ ) having no group having active hydrogen is, for example, a group having one addition-polymerizable double bond and having active hydrogen.
  • examples thereof include (meth) atalinoleic acid compounds that do not have and styrene compounds that have one addition polymerizable double bond and do not have a group having active hydrogen.
  • (meth) acrylic acid compounds include methyl (meth) acrylate, ethyl (meth) acrylate, ⁇ -propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth).
  • examples of (meth) acrylic acid compounds having one addition polymerizable double bond and no active hydrogen group include (meth) acrylic oxide compounds having a silsesquioxane skeleton.
  • Specific examples of (meth) acrylic acid compounds having a strong silsesquioxane skeleton include 3- (3,5,7,9,11,13,15-heptaethylpentacyclo [9.5.1. . 1 3,9 .1 5,15 I 7 ' 13 Koo Kuta siloxane - Bok I) propyl (meth) Atari rate, 3- (3,5,7,9,11,13,15- Heputai Sobuchiru - pentacyclo [9 ⁇ 5. 1.
  • styrene compound having one addition polymerizable double bond and no active hydrogen group examples include styrene, butyltoluene, ⁇ _methylstyrene, ⁇ -chlorostyrene, and the like. It is.
  • Examples of the styrene compound having one addition polymerizable double bond and having no active hydrogen group further include a styrene compound containing silsesquioxane.
  • Examples of styrene derivatives containing force, or silsesquioxane include ⁇ (4-Buylphenyl) -3, 5,7,9,11,13,15-heptaethylpentacyclo [9 ⁇ 5. 1.
  • I 3, .. 9 I 5,15 I 7 ' 13] Okutashiroki San,; L-(4-Byurufue two Honoré) -3,5,7,9,11, 13,15_ hepta isobutyl penta cyclo [9 • 5. 1 .
  • I 3,9 I 5,15 I 7 '13 O Kuta siloxanes, and; 1- (4 - Byurufueniru) -3,5, 7, 9, 11, 13 - hepta phenyl penta cyclo [.. 9. 5.
  • I 3,9 I 5,15 I 7 '13 such as O Kuta siloxane, 4-bi Yurufe two Le group Octasiloxane having (silical silsesquioxane); and 3- (3,
  • polymerizable monomer ( ⁇ ) a main chain derived from styrene, (meth) acrylic acid ester, siloxane, alkylene oxide (for example, ethylene oxide, propylene oxide) or the like is used. And a macromonomer having one polymerizable double bond.
  • Examples of the addition polymerizable monomer ( ⁇ ) include a compound having two addition polymerizable double bonds. n5.
  • styrene (meth) acrylic acid ester, siloxane, and alkylene oxide, such as ethylene oxide and propylene oxide, have a main chain induced by force, and a macromonomer having two polymerizable double bonds is also exemplified.
  • alkylene oxide such as ethylene oxide and propylene oxide
  • Examples of the addition polymerizable monomer ( ⁇ ) include compounds having three or more addition polymerizable double bonds.
  • styrene, (meth) acrylic acid ester, siloxane, and alkylene oxide, such as ethylene oxide and propylene oxide have a main chain induced by force, and also include macromonomers having three or more polymerizable double bonds. Is done.
  • Examples of the addition polymerizable monomer ( ⁇ ) include a compound containing fluorine.
  • the compound containing fluorine may be any of a butyl compound having a fluorine atom, a vinylidene compound, or a vinylene compound as long as the compound has a fluorine atom group and an addition polymerizable double bond in the molecule.
  • An acrylic acid derivative or a styrene derivative having a fluorine atom is preferable.
  • addition polymerizable monomer having a fluorine atom include, for example, fluoroalkyl (meth) acrylate, fluorostyrene, and fluorine-containing polyether compounds.
  • Examples of such an addition polymerizable monomer having a fluorine atom are JP-A-10-251352, JP2004-043671, JP-A-2004-155847, JP-A-2005-029743, JP-A-2006-117742, JP-A-2006. And the monomers disclosed in JP-A-299016 and JP-A-2005-350560.
  • fluoroalkyl (meth) acrylate examples include 2, 2, 2-trifluoroethyl (meth) acrylate, 2, 2, 3, 3-tetrafluoro ⁇ -propyl (meth) acrylate, 2, 2 , 3, 3—Tetrafunole, t—Pentinole (meth) acrylate, 2, 2, 3, 4, 4, 4—Hexafluorobutyl (meth) acrylate, 2, 2, 3, 4, 4, 4 —Hexafluoro-t-hexyl (meth) atarylate, 2, 3, 4, 5, 5, 5—Hexafoleore low 2,4-bis (Trifnore lometinole) pentyl (meth) atarylate, 2, 2 , 3, 3, 4, 4—Hexafluorobutyl (meth) acrylate, 2, 2, 2, 2 ', 2', 2 '—Hexafanole low isopropynole (meth) acrylate, 2 , 2, 3, 3, 4, 4,
  • Kuchinole (meta) attalate 3, 3, 4, 4 , 5, 5, 6, 6, 7, 7, 8, 8, 8—Tridekafunore Talent Kuchinole (meta) Atarirate, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7 , 7, 7 Tridekafunore talented heptinore (meth) atelierate, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10 — Hexadeca Funore Rodecinore (meth) attalate, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 10 , 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 11, 11 1-year-old Kutadekafunore-aged Lode De Sinole (Meta) Atari Relay, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 11, 11, 11—Nona Decahunore Age Lodecinole (Meta) Attalate, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 11, 11, 12, 12 Eikosaf
  • Examples include tylene.
  • fluorine-containing polyether compound examples include 1H, 1H-perfluoro-3, 6-dioxaheptyl (meth) acrylate, 1H, 1H-perfluoro-3, 6-dioxaoctyl (meth) acrylate, 1H, 1H-perfluoro- 3, 6-dioxadecanyl (meth) atalylate, 1H, 1H-perfluoro- 3, 6, 9 trioxadecanyl (meth) acrylate, 1H, 1H-perfluoro 3, 6, 9-trioxane decanyl ( 1), 1H-perfluorinated 3, 6, 9-trioxatridecanyl (meth) acrylate, 1H, 1H — perfluorinated 3, 6, 9, 12 tetraoxatridecanyl (meth) attalylate 1H, 1 ⁇ —perfluoro-3, 6, 9, 12 tetraoxatridecanyl (meth)
  • Such an addition polymerizable monomer having a fluorine atom can also be synthesized by reacting a fluorine compound having a hydroxyl group with an acid halide having an addition polymerizable functional group.
  • Fluorine compounds having such hydroxyl groups include (HO) C (CF) CH, (HO) C (C
  • the fluorine compound having a hydroxyl group can be synthesized and used, and a synthetic method is described in JP-A-10-147639.
  • Examples of the addition polymerizable monomer ( ⁇ ) include a compound having a hydrophilic group.
  • an oxyalkylene group-containing monomer such as methoxypolyethylene glycol mono (meth) acrylate.
  • the addition polymerizable monomer ( ⁇ ) may be used alone or in combination of two or more. When a plurality of types are used in combination, various composition ratios can be appropriately adjusted and used according to the specification of the target polymer.
  • the polymer of the present invention comprises a structural unit (structural unit ( ⁇ )) derived from fluorosilsesquioxane ( ⁇ ) having one addition polymerizable functional group in the molecule, and an organopolysiloxane (0) having an addition polymerizable functional group.
  • the structural unit derived from the structural unit (structural unit ( ⁇ )) and the structural unit derived from the addition polymerizable monomer ( ⁇ ) containing a group having active hydrogen (the structural unit (C)) are essential components.
  • the addition copolymer may be an ordered copolymer such as block copolymer or a random copolymer, but is preferably a random copolymer.
  • the polymer of the present invention may have a cross-linked structure or may be a graft copolymer.
  • the proportion of the structural unit (C) contained in the polymer of the present invention is not particularly limited, and the polymer of the present invention is a binder for the purpose of binding with a binder resin blended when used as a coating agent. It only needs to contain a group having active hydrogen to such an extent that preferable reactivity with the resin monomer can be obtained.
  • the polymer of the present invention further contains an arbitrary structural unit (D), the above molar ratios of the structural unit (A), the structural unit (B) and the structural unit (C) included in the polymer of the present invention. Is the same.
  • the weight average molecular weight of the polymer of the present invention varies depending on the content of the structural unit (B) and the like, and is about 1000 to 1 million as a guide.
  • the molecular weight distribution (Mw / Mn) of the polymer of the present invention is about 1.01-2.5 as a guide.
  • Fluorosylsesquioxane ( ⁇ ) having one addition-polymerizable functional group, organopolysiloxane (/ 3) having an addition-polymerizable functional group, and a group having active hydrogen in the molecule When more than one type of monomer is used as the addition polymerizable monomer ( ⁇ ) or any addition polymerizable monomer ( ⁇ ) that can be used as necessary, the ratio of each monomer May be appropriately determined according to the properties of the intended copolymer. In view of simplicity and versatility, radical copolymerization is preferred.
  • the addition polymerization can be performed using a polymerization initiator.
  • polymerization initiators used include 2,2'-azobisisoptyronitrile, 2,2'-azobis ( 2,4-dimethylvaleronitrile), 2,2'-azobis (2-butyronitrile), dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis (cyclohexane-carbocarbyl) ) And other compounds; benzoyl peroxide, lauryl peroxide, otatanyl peroxide, acetyl chloride, di-t-butyl peroxide, t-butyl tamil peroxide, dicumyl Radicals such as peroxides, peroxides such as t-butylperoxyacetate, t-butylperoxybenzoate, t-butylperoxyneodecanoate; and dithiocarbamates such as tetraethylthiuramdisulfide;
  • the polymerization initiator is p3 ⁇ 4.
  • examples of the polymerization reaction include living radical polymerization and active energy ray polymerization.
  • Living radical polymerization is represented by atom transfer radical polymerization; reversible addition-fragmentation chain transfer; iodine transfer polymerization; iniferter polymerization, and can be performed using a polymerization initiator described in the following references A to C. .
  • Cited reference A Supervision by Mikiharu Konoike and Go Endo, radical polymerization handbook, published on August 10, 1999, published by NT.
  • Active energy ray polymerization can be carried out using the compound described in the cited document D as an active energy ray polymerization initiator.
  • Cited reference D Photopolymer social gathering edition, Photosensitive material list book, published on March 31, 1996.
  • the active energy ray means an energy ray that can generate an active species by decomposing a compound that generates an active species.
  • active energy rays include optical energy rays such as visible light, ultraviolet rays, infrared rays, X rays, ⁇ rays, / 3 rays, ⁇ rays, and electron rays.
  • active energy ray polymerization initiator to be used are not particularly limited as long as they are compounds that generate radicals upon irradiation with ultraviolet rays or visible rays! Active energy ray
  • the compounds used as polymerization initiators include benzophenone, Michler's ketone, 4,4'-bis (jetylamino) benzophenone, xanthone, thixanthone, isopropyl xanthone, 2,4-jetylchital xanthone, 2-ethylanthraquinone, acetophenone, 2 -Hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl--isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetof Enone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzan
  • the amount of the polymerization initiator used in the above addition polymerization may be about 0.01 to 10 mol% with respect to the total number of moles of monomers.
  • a chain transfer agent may be used.
  • the molecular weight can be appropriately controlled by using a chain transfer agent.
  • chain transfer agents include thionaphthol, thiophenol, butyl mercaptan, ethylthioglycolate, mercaptoethanol, mercaptoacetic acid, isopropyl mercaptan, t-butyl mercaptan, dodecane thiol, thiomalic acid, pentaerythritol tetra (3 -Mercaptans such as mercaptopropionate) and pentaerythritol tetra (3-mercaptoacetate); disulfides such as diphenyl disulfide, jetyl dithiodalicolate, and jetyl disulfide; Butyrate, carbon tetrachloride, isopropylbenzene, jetyl ketone, black mouth form, ethyl
  • Chain transfer agents can be used alone or in admixture of two or more.
  • the specific production method of the polymer of the present invention may be the same as the production method of a normal addition polymer, for example, solution polymerization method, emulsion polymerization method, suspension polymerization method, bulk polymerization method, A bulk suspension polymerization method or a polymerization method using supercritical CO can be used.
  • solvents used in the above polymerization reaction include hydrocarbon solvents (benzene, toluene, etc.), ether solvents (jetyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, etc.), halogenated Hydrocarbon solvents (methylene chloride, black mouth form, black mouth benzene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (methanol, ethanol, propanol, isopropanol, butyl alcohol) , T-butyl alcohol, etc.), nitrile solvents (acetonitrile, propionitrile, benzonitrile, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), carbonate solvents (ethylene carbonate, propylene carbonate, etc.), Amide-based solvents (N, N, N-based solvent
  • the reaction temperature is not particularly limited, and it is preferably about 0 to 200 ° C, preferably room temperature to about 150 ° C.
  • the polymerization reaction can be performed under reduced pressure, normal pressure, or increased pressure, depending on the type of monomer and the type of solvent.
  • the polymerization reaction is preferably performed in an atmosphere of an inert gas such as nitrogen or argon.
  • the generated radicals are deactivated by contact with oxygen, and the decrease in polymerization rate is suppressed. This is to obtain a polymer whose amount is appropriately controlled.
  • the polymerization reaction is preferably carried out in a polymerization system from which dissolved oxygen is removed under reduced pressure (after removing dissolved oxygen under reduced pressure, the polymerization reaction may be carried out directly under reduced pressure! Lol.)
  • the polymer obtained in the solution may be purified or isolated by a conventional method, or may be used for forming a coating film as it is.
  • a purification method by reprecipitation operation is preferred.
  • This refining method is performed as follows. First, in the polymerization reaction solution containing the polymer and the unreacted monomer, a solvent that does not dissolve the polymer but dissolves the unreacted monomer, a so-called precipitant is added to this solution to remove only the polymer. Precipitate.
  • the preferred amount and use amount of the precipitating agent is 20 to 50 times based on the weight of the polymerization reaction solution.
  • a preferred precipitant is a solvent that is compatible with the solvent used in the polymerization, does not dissolve the polymer at all, dissolves only the unreacted monomer, and has a relatively low boiling point.
  • preferred precipitating agents are lower alcohols and aliphatic hydrocarbons. Particularly preferred precipitating agents are methanol, ethanol, 2-propanol, hexane, and heptane. These may be used alone or in combination of two or more.
  • Solmix AP-1, A-11, etc. commercially available as denatured alcohol, may be purchased from Nippon Alcohol Sales Co., Ltd.
  • the number of reprecipitation operations may be increased. By this method, only the polymer can be precipitated in a poor solvent, and the unreacted monomer and the polymer can be easily separated by a filtration operation.
  • the polymer of the present invention can be used for any application, but if necessary, combined with other resins (hereinafter referred to as binder resins) or resin monomers (hereinafter referred to as binder resin monomers).
  • binder resins resins
  • resin monomers resin monomers
  • it can be dissolved or dispersed in various solvents and used as a surface modifier (so-called “Coating IJ”).
  • a binder resin having a functional group capable of reacting with the polymer hereinafter referred to as a reactive binder resin
  • a component that crosslinks the polymer and the reactive binder resin by a reaction The polymer can be more firmly fixed to the base material via the binder resin.
  • selecting the binder resin having these characteristics does not impair the original characteristics of the resin.
  • the surface can be modified
  • the polymer of the present invention may be used alone as a surface modifier as described in 1) above, but it is mixed with other binder resin as described in 2) above to modify the surface. As described in 3) above, it can be used as an agent and mixed with a binder resin monomer that can react with the polymer of the present invention (hereinafter also referred to as a reactive binder resin monomer) to modify the surface. It may be used as an agent.
  • a binder resin monomer that can react with the polymer of the present invention (hereinafter also referred to as a reactive binder resin monomer) to modify the surface. It may be used as an agent.
  • the substrate surface can be directly modified.
  • the hydrogen bonding force of the active hydrogen contained in the polymer of the present invention works, and the effect of improving the adhesion to the substrate can be obtained.
  • the binder resin may be a plurality of types of resins that may be either thermoplastic resins or thermosetting resins.
  • binder resin examples include polyethylene, polypropylene, polybutyl chloride, polyvinylidene chloride, polystyrene, acrylonitrile monostyrene resin, acrylonitrile monobutadiene-styrene resin, poly (meth) acrylate resin, ultra high molecular weight polyethylene, poly-4.
  • polyetherimide polyamideimide
  • phenol resin alkyd resin
  • melamine resin epoxy resin
  • epoxy resin urea resin
  • bismaleimide resin polyester urethane resin
  • polyether urethane polyether urethane
  • emission resins and silicone resins include.
  • the polymer of the present invention may be used by mixing with a reactive binder resin monomer.
  • a polymer of the present invention having a group having active hydrogen and a reactive binder-resin monomer are mixed and used, the resin obtained by curing and the polymer of the present invention are cross-linked, As a result, it is possible to obtain a composite tree with excellent mechanical properties, surface / interface characteristics, and compatibility.
  • a solution containing the polymer of the present invention having a group having active hydrogen, a reactive binder resin monomer, and a curing reaction initiator as necessary is applied to the substrate, and the coating film is dried. And by curing, a film (composite film) made of a composite resin with a binder resin can be formed on the substrate.
  • the polymer of the present invention when used in combination with a binder resin or a binder-one resin monomer as in 2) and 3), the polymer of the present invention in a solution or dispersion containing these.
  • the weight ratio of the binder resin or binder resin monomer is preferably 0.01: 99.99 to 80:20.
  • the reactive binder resin monomer may be a thermoplastic resin monomer or a thermosetting resin monomer! /, And a preferred example is a single monomer that forms a urethane resin.
  • the body is included.
  • examples of the reactive binder resin monomer include compounds having a plurality of isocyanate groups as shown below.
  • Examples of the compound having a plurality of isocyanate groups include low molecular weight polyisocyanates such as aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, prepolymers, and the like. Examples thereof include isocyanurate bodies, trione bodies, and derivatives and modified bodies of these polyisocyanates.
  • Aliphatic polyisocyanates include diisocyanates (e.g. trimethylene diisocyanate).
  • C-alkane diisocyanates such as sulfonate, hexamethylene diisocyanate, pentamethylene diisocyanate, 2, 4, 4— or 2, 2, 4 trimethyl hexamethylene diisocyanate
  • polyisocyanate eg, lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-trii
  • Alicyclic polyisocyanates include diisocyanates (eg, 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5 , 5-Trimethylcyclohexyl isocyanate (common name: isophorone diisocyanate), 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4 cyclohexanediisocyanate, methyl-2,6 cyclohexanone Xanthodiisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane (common name: hydrogenated xylylene diisocyanate) or a mixture thereof, norbornane diisocyanate, etc., polyisocyanate (E.g., 1,3,5-triisocyanatocyclohexane, 1,3,
  • the araliphatic polyisocyanates include diisocyanates (e.g., 1,3— or 1,4 xylylene diisocyanate or mixtures thereof, ⁇ , ⁇ ′ diisocyanate 1,4 jetylbenzene, 1,3—or 1, 4 Bis (1 isocyanato 1-methylethyl) benzene (common name: tetramethylxylylene diisocyanate) or a mixture thereof, polyisocyanate (for example, triisocyanate such as 1,3,5-triisocyanatomethylbenzene) Is mentioned.
  • Aromatic polyisocyanates include diisocyanates (eg, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5 naphthalene diisocyanate, 2, 4 'or 4, 4'-diphenylmethane diisocyanate or mixtures thereof, 2, 4 or 2, 6 tolylene diisocyanate or mixtures thereof, 4, 4' toluidine diisocyanate, 4, 4 '-Diphenyl ether diisocyanate), polyisocyanate (eg, triphenylmethane 1, 4, 4', 4 "-triisocyanate, 1, 3, 5 triisocyanate benzene, 2, 4, 6 tris Triisocyanates such as isocyanatotoluene, for example, tetraisocyanates such as 4,4'-diphenylmethane-1,2,2 ', 5,5'-tetraisocyanate
  • polyisocyanate derivatives include, for example, the reaction of the polyisocyanate dimer, trimer (isocyanurate ring-containing polyisocyanate), biuret, allophanate, carbon dioxide and the above polyisocyanate monomer.
  • modified polyisocyanate examples include, for example, the above-mentioned polyisocyanate or a polyisocyanate derivative and a low molecular weight polyol or a low molecular weight polyamine described later, and the isocyanate group of the polyisocyanate is a hydroxyl group or a low molecular weight polyol.
  • examples include polyol-modified products and polyamine-modified products obtained by reacting at an equivalent ratio that is in excess of the amino group of the low molecular weight polyamine.
  • the reactive binder resin monomer used in the present invention includes a urethane resin having an isocyanate group.
  • Urethane resins having such isocyanate groups are commercially available as Coronate Millionate from Nippon Polyurethane Industry Co., Ltd., Takenate from Mitsui Chemicals Polyurethane Co., Ltd., and MT Olester. May be used.
  • polyhydric alcohols examples include polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, and hydrogenated polybutadiene polyols.
  • polyether polyols include polyethylene glycol, polypropylene glycol, poly (ethylene / propylene) glycol, polytetramethylene ether glycol and the like.
  • polyester polyol examples include a compound obtained by polycondensation of a low molecular weight diol and a dibasic acid, and a compound obtained by a ring opening reaction of a dibasic acid using a low molecular weight diol as an initiator.
  • Low molecular weight diols include ethylene glycol, diethylene glycolol, triethylene glycolanol, propylene glycolanol, 1,4 butanediole, 3-methinoleol 1,5-pentanediole, 1,6-hexanedioleol, neopentinoleglycol And the like.
  • dibasic acid used for the former polycondensation examples include adipic acid, azelaic acid, sebacic acid, isophthalic acid, and terephthalic acid. And the latter Examples of the dibasic acid used in the ring-opening reaction include poly ⁇ -force prolatatatone and poly 13-methyl- ⁇ -valerolatatone.
  • polycarbonate polyol examples include 1,6-hexanediol polycarbonate polyol, 3-methyl-1,5-pentanediol polycarbonate polyol, and mixed diol polycarbonate polyol having 4 to 6 carbon atoms.
  • polybutadiene polyol examples include polyols composed of 1,4 polybutadiene and 1,2-polybutadiene.
  • hydrogenated polybutadiene polyol include those having a paraffin skeleton obtained by hydrogenating polybutadiene polyol.
  • the blending ratio of the polymer of the present invention and the compound having an isocyanate group may be arbitrary, but it is preferable that the equivalent of ⁇ group / NCO group is 0;
  • a urethanization catalyst for the purpose of accelerating the curing reaction of the polymer of the present invention containing a group having active hydrogen and a reactive binder resin monomer to form a urethane resin, it is possible to use a urethanization catalyst as a curing reaction initiator. it can.
  • urethanization catalysts examples include organometallic urethanization catalysts and tertiary amine urethanization catalysts.
  • Organometallic urethanization catalysts include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octanoate, lead naphthenate, nickel naphthenate, naphthene Mention may be made of organometallic urethanization catalysts such as cobalt acid.
  • Tertiary amine amine urethanation catalysts include triethylenediamine, ⁇ , ⁇ , ⁇ ', ⁇ ', ⁇ '-pentamethyldipropylenetriamine, ⁇ , ⁇ , ⁇ ', ⁇ ', ⁇ '-penta Methyljetylenetriamine, ⁇ , ⁇ , ⁇ ', N' Tetramethylhexamethylenediamine, bis (dimethylaminoethyl) ether, 2- ( ⁇ , ⁇ dimethylenoleamino) -ethylenole 1— ( ⁇ , ⁇ Dimethylamino) propyl ether, ⁇ , N 'dimethylcyclohexylamine, ⁇ , ⁇ dicyclohexylmethylamine, methylenebis (dimethylcyclohexyleno) amine, triethynoleamine, ⁇ , ⁇ ⁇ ⁇ ⁇ dimethylacetylamine, ⁇ , ⁇
  • the catalyst can be used in any amount with respect to the resin composition, but preferably 0.000; 20% based on the mass of the resin composition; more preferably 0.00; 10%
  • the polymer of the present invention can be dissolved or dispersed in a solvent and used as a surface modifier.
  • concentration of the solid content (including the polymer of the present invention and other resins) contained in the surface modifier is not particularly limited, but may be about 0.0;! To 50% by weight.
  • the solvent for dissolving or dispersing the polymer of the present invention is the polymer of the present invention
  • Any solvent that is inert with respect to the isocyanate group contained in the reactive matrix monomer may be used, for example, aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, methyl Ketone solvents such as ethyl ketone and cyclohexanone, ethylene glycol ether ether acetate, propylene glycol methyl ether acetate, daryl ether ether solvents such as ethyl 3-ethoxypropionate, tetrahydrofuran, dioxane, etc.
  • Ether solvents dimethylformamide, dimethylacetate Amides, ⁇ ⁇ ⁇ Methy
  • the reactive binder resin monomer may also include a monomer that forms a melamine resin.
  • Examples of the monomer that forms the melamine resin include alkyl etherified melamine resins. Specific examples include methylolated aminotriazine and alkyl etherified with cyclohexanol or C1-6 alkanol. More specifically, methyl etherified melamine resin, butyl etherified melamine resin, Examples include methylbutyl mixed monotelomerized melamine resin.
  • the method for applying the solution containing the polymer of the present invention to the substrate is not particularly limited, but spin coating method, roll coating method, slit coating method, date coating method, spray coating method, gravure coating method, reverse coating method.
  • substrates to be applied include transparent glass substrates such as white plate glass, blue plate glass, and silica coated blue plate glass; polycarbonate, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, polyamideimide, polyimide, triacetate, diacetate Synthetic resin sheet, film, etc .; cycloolefin resin including norbornene resin (trade name: ZENOOR, ZEONEX, Nippon Zeon Co., Ltd., trade name: ARTON, JSR Corporation), metathalyl styrene, polysulfone, alicyclic Transparent resin substrates used for optical applications such as acrylic resin and polyarylate; Metal substrates such as aluminum plates, copper plates, nickel plates, and stainless steel plates; Other ceramic substrates, semiconductor substrates having photoelectric conversion elements; urethane rubber, styrene rubber, etc. Cited It is.
  • pretreatment examples include chemical treatment with a silane coupling agent, sandblast treatment, corona discharge treatment, ultraviolet treatment, plasma treatment, ion plating, sputtering, gas treatment. Phase reaction method, vacuum deposition, etc. are included.
  • the applied solution can be dried in an environment of room temperature to about 200 ° C.
  • the coating solution is produced by mixing and dissolving the polymer of the present invention and, if necessary, optional components in the solvent.
  • the use of the film of the present invention is as follows: release paper, film for release film, water repellent Examples thereof include a film, an antifouling film, a sliding film, an antireflection film, and an insulating film.
  • release paper film for release film
  • water repellent examples thereof include a film, an antifouling film, a sliding film, an antireflection film, and an insulating film.
  • a 1-L four-necked flask equipped with a reflux condenser, thermometer, and dropping funnel was added to a trifnore-proprietary propylene lime xysilane (l OOg), THF (500 mL), deionized water (10.5 g) ) And sodium hydroxide (7.9 g) were added, and the mixture was heated with an oil bath to room temperature and to a temperature at which THF was refluxed while stirring with a magnetic stirrer. Stirring was continued for 5 hours from the start of reflux to complete the reaction. Thereafter, the flask was lifted from the oil bath and allowed to stand at room temperature for 1 hour, then set again in the oil bath and concentrated by heating under a constant pressure until a solid precipitated.
  • the precipitated product was collected using a pressure filter equipped with a membrane filter having a pore size of 0.5 m. Next, the obtained solid was washed once with THF and dried in a vacuum dryer at 80 ° C. for 3 hours to obtain 74 g of a colorless powdery solid.
  • Example 1 0.1 g of the polymer (al) obtained in Example 1 was dissolved in 9.9 g of a fluorine-based solvent (Asahi Glass Products AK225) to obtain a coating solution.
  • the obtained coating solution was spin-coated on a polymethylmetatalylate (PMMA) substrate at 3000 rpm for 30 seconds and dried at 70 ° C. for 30 seconds to obtain a film.
  • PMMA polymethylmetatalylate
  • Test Example 1 except that the polymer (al) obtained in Example 1 was changed to 0.05 g and AK225 was changed to 9.95 g. A film was obtained in the same manner as above.
  • a film was obtained in the same manner as in Test Example 1 except that the polymer (al) obtained in Example 1 was changed to 0.01 g and AK225 was changed to 9.99 g.
  • Acrylic pressure-sensitive adhesive tape (Nitto Denko No. 31B) was bonded to the obtained film surface, and after pressure bonding with a 2 kg pressure roller, the acrylic pressure-sensitive adhesive tape was peeled off. This operation was repeated a total of 10 times to evaluate the substrate adhesion. The substrate adhesion of the resulting film was evaluated by measuring the contact angle before and after the adhesion test and calculating the surface free energy (Table 2).
  • the fluorine concentration in the resin solid content of the obtained coating agent was 0.01% by weight, and the silicone concentration in the resin solid content was 0.02% by weight.
  • “Fluorine concentration in resin solids” and “silicone concentration in resin solids” are included in the polymer solution with respect to the total solids weight of the polymer solution containing polymer (a4) and melamine resin. It means the ratio of fluorine and silicone weight, and was calculated from the weight ratio of the same polymer solution and melamine resin.
  • the weight average molecular weight determined by GPC analysis of the polymerization solution was 30,800, and the molecular weight distribution was 1.58.
  • the obtained coating solution was coated on a stainless steel plate (SUS304, length 130mm ⁇ width 70mm ⁇ thickness 0.5mm) using a coating rod (# 9, manufactured by R. D. Specialties).
  • the obtained coating film was dried at the same time as curing at 160 ° C for 20 minutes in a high-temperature chamber to obtain a transparent film having a film thickness of about 10.
  • [0081] Preparation of melamine-based film A coating solution was prepared in the same manner as in Example 7 except that the polymer solution containing the polymer (bl) obtained in Comparative Example 1 was used instead of the polymer solution containing the polymer (a4). A ⁇ film was obtained. The fluorine concentration in the resin solid content of the obtained coating liquid was 0.01% by weight, and the silicone concentration in the resin solid content was 0.02% by weight.
  • a coating solution was prepared in the same manner as in Example 7 except that the polymer solution containing the polymer (b2) obtained in Comparative Example 2 was used instead of the polymer solution containing the polymer (a4). A ⁇ film was obtained.
  • the resulting coating solution had a fluorine concentration in the resin solid content of 0.01% by weight, and a silicone concentration in the resin solid content of 0.01% by weight.
  • a coating solution was prepared in the same manner as in Example 7 except that the polymer solution containing the polymer (b3) obtained in Comparative Example 3 was used instead of the polymer solution containing the polymer (a4). A ⁇ film was obtained.
  • the resulting coating solution had a fluorine concentration in the resin solid content of 0.01% by weight, and a silicone concentration in the resin solid content of 0.01% by weight.
  • the obtained coating agent was applied on a stainless steel plate (SUS304, length 130 mm ⁇ width 70 mm ⁇ thickness 0.5 mm) by spray coating.
  • the obtained coating film was dried simultaneously with curing at 120 ° C. for 30 minutes in a high-temperature chamber to obtain a transparent coating film having a thickness of about 10 ⁇ .
  • the fluorine concentration in the resin solid content of the obtained coating liquid was 0.01% by weight, and the silicone concentration in the resin solid content was 0.02% by weight.
  • a coating solution was prepared in the same manner as in Example 9 except that the polymer solution containing the polymer (bl) obtained in Comparative Example 1 was used instead of the polymer solution containing the polymer (a4). ⁇ film Obtained.
  • the fluorine concentration in the resin solid content of the obtained coating liquid is 0.01% by weight.
  • the silicone concentration in the resin solids was 0.02% by weight.
  • a coating solution was prepared in the same manner as in Example 9 except that the polymer solution containing the polymer (b2) obtained in Comparative Example 2 was used instead of the polymer solution containing the polymer (a4). A ⁇ film was obtained.
  • the fluorine concentration in the resin solid content of the obtained coating liquid is 0.01% by weight.
  • the silicone concentration in the resin solids was 0.01% by weight.
  • a coating solution was prepared in the same manner as in Example 9 except that the polymer solution containing the polymer (b3) obtained in Comparative Example 3 was used instead of the polymer solution containing the polymer (a4). A ⁇ film was obtained.
  • the fluorine concentration in the resin solid content of the obtained coating liquid is 0.01% by weight.
  • the silicone concentration in the resin solids was 0.01% by weight.
  • Acrylic adhesive tape (Nitto Denko No. 31B) and silicone adhesive tape (3M No. 8911) are bonded to the surface of the film release layer and pressed with a 2 kg pressure roller, and the pressure is also 24 hours later.
  • the peel strength with the layer was measured with a tensile tester.
  • Acrylic adhesive tape (Nitto Denko No. 31B) and silicone adhesive tape (3M No. 8911) were bonded to the surface of the film release layer and pressed with a 2 kg pressure roller, and the pressure was also left at room temperature for 30 minutes. Next, after adding a heat history for 1 hour in a high-temperature chamber at 130 ° C, it was allowed to cool for 30 minutes, and the peel force between the release layer and the adhesive layer was measured with a tensile tester.
  • the surface property tester HEIDON Type: 14W (manufactured by Shinto Chemical Co., Ltd.) was used for measurement according to JIS K5400.
  • Tables 3 and 4 show the physical properties and evaluation results of the films obtained.
  • thermosetting film can be obtained by performing the same operation as in Example 9 except that the polymer (al) obtained in Example 1 was used instead of the polymerization solution containing the polymer (a4). it can.
  • thermosetting film is obtained by performing the same operation as in Example 9, except that the polymer (a3) that can be obtained in Example 3 is used instead of the polymer solution containing the polymer (a4).
  • Can [0093] (Consideration of evaluation results such as test examples)
  • Table 2 shows that Examples 4, 5 and 6 show good adhesion to the substrate.
  • Example 8 using a fluorosilsesquioxane compound is more preferable than Comparative Examples 4 to 6 using other fluorine compounds.
  • the coefficient of dynamic friction was kept low for slipperiness with high water repellency and oil repellency, and the result of repelling magic ink was obtained for stain resistance. This is due to the excellent blooming properties of the fluorosilsesquioxane compound, not only the function of the fluorosilsesquioxane compound, but also the excellent features of the organopolysiloxane present in the same molecule. It is suggested that
  • Example 9 exhibits better surface properties, slipperiness, and contamination resistance than Comparative Examples 7-9.
  • the polymer and the surface modifier of the present invention may be used for specific purposes such as prevention of toner sticking or charge enhancement, imparting a non-adhesive function to a fixing roller, a mag roller, a rubber roller, etc.
  • Resin for optical applications used for surface modifiers for electronic copying machine members such as imparting a sliding function to peeling nails, surface top modifiers for automobiles, hard coats, lenses, etc.
  • Antifouling treatment agent antifogging treatment agent, antifouling treatment agent for building materials such as wall materials and flooring materials
  • vertical mold release treatment agent used in nanoimprinting, resist material modifier, printed circuit board
  • Water-repellent 'waterproofing agent protective film used for displays
  • antifouling agent for protective film antifouling agent for touch panel
  • surface modifier for preventing fingerprint adhesion imparting peeling function to films such as polyester
  • the It can be used as a mold release treatment agent, and it can diversify various properties and applications.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Paints Or Removers (AREA)
  • Silicon Polymers (AREA)

Abstract

La présente invention concerne un polymère contenant une unité structurelle A dérivée d'un fluorosilsesquioxane qui comporte un groupe fonctionnel polymérisable par addition dans une molécule, une unité structurelle B dérivée d'un organopolysiloxane qui comporte un groupe fonctionnel polymérisable par addition, une unité structurelle C dérivée d'un monomère polymérisable par addition qui contient un groupe comportant un hydrogène actif, et éventuellement une unité structurelle D dérivée d'un monomère polymérisable par addition, différent du fluorosilsesquioxane qui comporte un groupe fonctionnel polymérisable par addition dans une molécule, ledit organopolysiloxane comportant un groupe fonctionnel polymérisable par addition et ledit monomère polymérisable par addition contenant un groupe qui comporte un hydrogène actif.
PCT/JP2007/074235 2006-12-15 2007-12-17 Polymère contenant du fluor et composition de résine WO2008072765A1 (fr)

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KR20097012338A KR101494347B1 (ko) 2006-12-15 2007-12-17 플루오르계 중합체 및 수지 조성물
AT07850723T ATE543846T1 (de) 2006-12-15 2007-12-17 Fluorhaltiges polymer und harzzusammensetzung
EP07850723A EP2096128B1 (fr) 2006-12-15 2007-12-17 Polymère contenant du fluor et composition de résine
JP2008549391A JPWO2008072765A1 (ja) 2006-12-15 2007-12-17 フッ素系重合体および樹脂組成物
US12/519,354 US7989560B2 (en) 2006-12-15 2007-12-17 Fluorine-containing polymer and resin composition

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US20120322264A1 (en) * 2010-02-24 2012-12-20 Basf Se Aqueous polishing agent and graft copolymers and their use in a process for polishing patterned and unstructured metal surfaces
JP2013525543A (ja) * 2010-04-23 2013-06-20 ヘンケル コーポレイション シリコーン−アクリルコポリマー
JPWO2016159023A1 (ja) * 2015-03-31 2017-07-13 Jnc株式会社 コーティング剤、皮膜、積層体、表面保護物品
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TWI622594B (zh) * 2016-03-17 2018-05-01 Lg Chem, Ltd. 多面體寡聚矽倍半氧烷與其製備方法、包括其的塗佈組成物及抗反射膜

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JP5051282B2 (ja) * 2010-07-22 2012-10-17 富士ゼロックス株式会社 ウレタン樹脂、定着用部材および画像形成装置
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JP5321721B2 (ja) * 2011-08-19 2013-10-23 富士ゼロックス株式会社 樹脂材料
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JP6587418B2 (ja) 2014-05-15 2019-10-09 キヤノン株式会社 電子写真用部材、プロセスカートリッジ及び電子写真装置
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KR102606542B1 (ko) * 2021-04-08 2023-11-24 인하대학교 산학협력단 투명 하드코팅막 제조용 조성물 및 투명 하드코팅막과 그 제조방법

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JP2010033000A (ja) * 2008-06-25 2010-02-12 Ricoh Co Ltd トナー及び現像剤
US20110054052A1 (en) * 2009-08-27 2011-03-03 Samsung Electronics Co., Ltd. Polyurethane foam composition and polyurethane foam prepared using same
US8748501B2 (en) * 2009-08-27 2014-06-10 Samsung Electronics Co., Ltd. Polyurethane foam composition and polyurethane foam prepared using same
US20120322264A1 (en) * 2010-02-24 2012-12-20 Basf Se Aqueous polishing agent and graft copolymers and their use in a process for polishing patterned and unstructured metal surfaces
US9005472B2 (en) * 2010-02-24 2015-04-14 Basf Se Aqueous polishing agent and graft copolymers and their use in a process for polishing patterned and unstructured metal surfaces
JP2013525543A (ja) * 2010-04-23 2013-06-20 ヘンケル コーポレイション シリコーン−アクリルコポリマー
US8962748B2 (en) 2010-04-23 2015-02-24 Henkel US IP LLC Silicone-acrylic copolymer
US9751286B2 (en) 2011-06-30 2017-09-05 Jnc Corporation Weather-resistant multilayer film
JPWO2016159023A1 (ja) * 2015-03-31 2017-07-13 Jnc株式会社 コーティング剤、皮膜、積層体、表面保護物品
TWI622594B (zh) * 2016-03-17 2018-05-01 Lg Chem, Ltd. 多面體寡聚矽倍半氧烷與其製備方法、包括其的塗佈組成物及抗反射膜
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EP2096128A4 (fr) 2011-04-13
KR20090100353A (ko) 2009-09-23
KR101494347B1 (ko) 2015-02-17
US20100093951A1 (en) 2010-04-15
ATE543846T1 (de) 2012-02-15

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